DE3105622A1 - METHOD FOR PRODUCING THIURAM DISULFIDES - Google Patents

Description

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ι Process for the preparation of thiuram disulfides j

A k ζ ο GmbH Wuppertal

The invention relates to a method for producing thiuram disulfides substituted with aliphatic, araliphatic and / or cycloaliphatic hydrocarbon radicals appropriately substituted amines and carbon disulfide in the presence of oxygen and a metal catalyst.

Thiuram disulfide .sind by known processes by oxidative Dimerization of salts of substituted dithiocarbamic acids available. As an oxidizing agent here Hydrogen peroxide, nitrogen dioxide, chlorine, bromine, iodine

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Ozone, oxygen, sodium nitrite, sodium hypochlorite / sulfur chloride, Potassium perbromate, selenic acid or ammonium persulfate can be used. For example, tetramethylthiuram disulfide, one of the most important representatives of this class of compounds, technically produced using a two-stage process, wherein in a first process stage dimethylamine and carbon disulfide in aqueous sodium hydroxide for Sodium-NiN-dimethyHithiocarbaitat- implemented and this in a second process stage either with hydrogen peroxide in the presence of sulfuric acid (BIOS 1150, Fiat 1018), means Chlorine (US patents 27 51 415 and 27 51 416) or electrolytically (DE-Offenlegungsschriften 28 02 260 and .. . 28 03 591) is oxidized.

A method is already known from DE-PS 12 26 564, after which a secondary alkyl, aryl or alkylaryl • amine with carbon disulfide in an aqueous or non-aqueous Medium by means of an oxygen-containing gas and a metal catalyst to the substituted thiuram disulfide is implemented. A sulfonated or carboxylated metal phthalocyanine of a metal serves as a catalyst VIII. Group of the periodic table, in particular Koebalt phthalocyanine. The yields in this process are comparatively low, in the best case they are around 25% d. Th. When using aromatic amines such as diphenylamine, no thiuram disulfide at all is produced the process of DE-PS 12 26 564 formed. Apart from that, the manufacturing and industrial application is this one Catalyst problematic.

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It is also known that in the oxidation of alkali salts of substituted dithiocarbamic acids by means of oxygen To use metal-containing catalyst: According to the method of DE-AS 11 65 Oll, the oxidation in the presence of a aqueous solution of a sulfonated or carboxylated metal phthalocvanin, the metal of which is from Group VIII of the periodic table is carried out at a pH of about 7 to 12. Disadvantage of this process is especially the high consumption of auxiliary materials, alkali to prepare the dithiocarbamates (e.g. 2 moles of NaOH per mole of thiuram disulfide) and acid to adjust the pH (e.g.

2 moles of HCl per mole of thiuram disulfide) and the formation large amounts of unusable by-products (2 mol NaCl per mol thiuram disulfide). Apart from that, the industrial The production and use of such catalysts is problematic. It is also already known to replace the alkali salts to use an ammonium salt of dithiocarbamic acid .. In the process of DE-OS 25 27 898 ammonium dimethyldithiocarbamate is used in aqueous solution in the presence of sulfuric acid at a pH of 5 to 7 using hydrogen peroxide oxidized. This gives a suspension of solid tetramethylthiuram disulfide in an aqueous ammonium sulfate solution. The process is disadvantageous in that it occurs after the solid tetramethylthiuram disulfide has been filtered off Accruing "filtrate must be concentrated to the limit of the solubility of the Ammorisulfat, then by means of Ammonia to precipitate the ammonium sulfate. Ammonium sulphate can be used, for example, as a fertilizer; it However, it is to be regarded as a disadvantage that in this process the preparation of the tetramethylthiuram disulfide is necessarily connected to a second product that can be assigned to a different industrial area. Apart from that

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of this, the ammonium sulphate is only used in agriculture to be used if it has been completely freed from adhering dithiocarbamate beforehand.

There was therefore a need to create a process for the preparation of thiuram disulphides that does not require auxiliary chemicals and that is not linked to the production of a by-product that is not desired in itself.

It has now been found, surprisingly, that the yield and selectivity in the oxidation of secondary amines with a pKa - 8 and carbon disulfide to thiuram disulfides can be increased considerably by means of oxygen if certain metals from other classes of Periodic table or derivatives thereof.

Gi. qenscand of the invention is thus a method of manufacture one with aliphatic, araliphatic and / or · cycloaliphatic Hydrocarbon radicals substituted thiuram disulfide by reacting an appropriately substituted secondary amine with carbon disulfide in a solvent and in the presence of oxygen or an oxygen-containing gas and a metal-containing catalyst / which is characterized is that the reaction with a secondary amine with a pK value of -8 and at temperatures from 0 to

3.

2OO ° C is carried out by

a) Carbon disulfide and the secondary amine in one Molar ratio of 1.0 to 1.2: 1 in the presence of Oxygen or an acidic gas and des metal-containing catalyst is implemented, or

b) first carbon disulfide and the secondary amine in a molar ratio of 0.9 to 1.1: 2.0 to 2.2 and

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then the reaction product obtained with 1.0 to 1.2 moles of carbon disulfide in the presence of oxygen or oxygen-containing gases and the metal-containing one Catalyst is implemented, or

c) Carbon disulfide and the secondary aminine are known per se Vfeise in a ratio of 0.9 to 1.1: 2.0 to 2.2 not used, the dithiocarbainate formed in a molar ratio of 1.0: 1.0 to 1.2 in the presence of oxygen or an oxygen-containing gas and the metal-containing gas Catalyst is implemented,

where the metal-containing catalyst is cerium, manganese, copper, molybdenum, vanadium or a derivative of the metals mentioned or a mixture thereof is used.

The method according to the invention is suitable for. Manufacturing a multitude of very differently substituted thiuram disulfides. · If one uses: iur a single secondary amine as Reaction partner, a thiuram disulfide is obtained, which have the same substituents on both nitrogen atoms wearing. In the case of a symmetrically substituted secondary amine, a thiuram disulfide with four identical ones is obtained Substituents. If two different secondary amines are used as reactants, one can, depending on the process conditions (Differences in basicity of the amines, molar ratios, etc.) Thiuram disulfide with. two differently substituted. Obtain nitrogen atoms; more or less large amounts of the two can be used as by-products symmetrically substituted thiuram disulfides are formed.

The metal-containing catalysts are cerium, manganese, copper, molybdenum or vanadium in elemental form or as salts, Oxides, complexes or in the form of their organic compounds

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used. Of the metals mentioned or their derivatives, they have copper, manganese and cerium compared to molybdenum and vanadium are the higher catalytic efficiency, however. Also the latter two metals and their derivatives excellent catalysts for oxidation.

Elemental copper is preferably used as copper powder. As a copper compound, all are mono- or bivalent inorganic, organic, simple or complex copper salts are considered. Examples of suitable worthwhile ones Copper salts are copper (I) chloride, bromide and iodide, addition compounds of these copper (I) halides with carbon monoxide, complex copper (I) salts, such as the alkali chlorocuprates, complex ammoniates d ^ s copper (I) cyanide, e.g. cyanocuprates such as potassium tricyanocuprate (I), double salts with copper (I) rhodanide, copper (I) acetate, copper (I) sulfide and complex double sulfides of copper (I) sulfide and alkali pole ysuLfiden. Examples of suitable copper (II) salts are Copper (II) chloride, bromide, sulfide, sulfate, nitrate, nitrite, rhodanide, cyanide, Cu (II) salts of carboxylic acids, such as copper (II) acetate, copper dithiocarbamate and the complex ammoniates of copper (II) salts. Copper (I) oxide is also very suitable as a catalyst.

Examples of suitable manganese-containing catalysts are manganese powder, manganese dioxide, potassium permanganates and manganese acetate and the manganese dithiocarbamates and the other copper compounds corresponding to the above Manganese derivatives. ■.

Examples of suitable cerium catalysts are metallic cerium, cerium dioxide, cerium (III) chloride, cerium (IV) chloride

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and the cerium chlorocomplex salts, cerium nitrate and the nitrate salts, Cerium sulfate, cerium carbonate, cerium oxalate and the cerium sulfides called.

Examples of suitable vanadium catalysts are the vanadium oxides, chlorides and sulfates and the known ones Double and complex salts.

Finally, examples of suitable molybdenum catalysts are the oxides, chlorides, sulfides and fluorides, also called the molybdates and the well-known complex acid salts.

Of course, mixtures of several of the mentioned catalysts are used. The required The amount of metal-containing catalyst is surprisingly small. It is preferably in the range from 0.01 to 5 mmol, based on to 1 mole of secondary amine or dithiocarbamate. Smaller amounts of catalyst can also be used long, but then longer response times have to be accepted. Higher amounts of catalyst are avoided because then there is a risk that the catalyst will precipitate and contaminate the reaction product.

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Aliphatic ^ suitable for the process according to the invention secondary amines are e.g. the following:

Dimethylamine, diethylamine, dipropylamine, diisopropylamine, Dibutylamine, di-sec-butylamine, di-tert-butylamine, Di- (2-methylpropyl) -amine, dipentylamine, di- (1-methylbutyl) -amine, Di (2-methylbutyl) amine, pi- (3-methylbutyl) amine, Di- (1.1-dimethylpropyl) -amine, di- (2.2-dimethylpropyl) -amine, Di- (1,2-dimethylpropyl) -amine, dihexylamine, di- (1-methylpentyl) -amine, Di- (2-methylpentyl) -amine, di- (3-methylpentyl) -amine, Di- (4-ethylpentyl) amine, di- (1,1-dimethylbutyl) amine, Di- (2.2-dimethylbutyl) -amine, di- (3.3-dimethylbutyl) -amine, Di- (2,3-dimethylbutyl) -amine, di- (l-ethylbutyl) -amine, Di- (2-ethylbutyl) amine, diheptylamine, Di- (1-methylhexyl) -amine, di- (2-methylhexyl) -amine, di- (3- ' methylhexyl) amine, di- (4-methylhexyl) amine, di- (5-methylhexyl) amine, Di- (1-ethylpentyl) amine, di- (2-ethylpentyl) amine, Di- (3-ethylpentyl) -amine, dioctylamine, di- (1-methylheptyl) -amine, Di- (2-methylheptyl) -amine, di- (3-methylheptyl) -amine, Di (4-methylheptyl) amine, di (5-methylheptyl) amine, Di- (6-methylheptyl) -amine, di- (I-ethylhexyl) -amine, Di- (2-ethylhexyl) -amine, di- (3-ethylhexyl) -amine, Di- (4-ethylhexyl) -amine / methyl-ethyl-amine, ethyl-butyl-amine, Dilaurylamine, Didodecylamine, Ditride.cylamin, Dipalmitylaiain, Distearylamine and dioleylamine.

Suitable cycloaliphatic secondary amines are, for example, the following:

Dicyclohexylamine, 4.4'-dimethyldicyclohexylamine, 3.3'-dimethyldicyclohexylamine, 2.2'-dimethyldicyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohoxylamine, N-isopropylcyclohexylamine, N-butylcyclohexylamine, N-sec-butylcyclohexylamine, N-tert-butyl-

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cyclohexylamine, N-pentylcyclohexylamine, N- (1-methylbutyl) -cyclohexylamine, N- (2-methylbutyl) -cyclohexylamine, N- (3-methylbutyl) -cyclohexylamine, N- (I.1-dimethylpropyl) -cyclohexylamine, N- (2. 2-DiTiethylpropyl) -cyclohexylamine, N- (1,2-dimethylpropyl) -cyclohexylamine, N-hexylcyclohexylamine, -N- (1-methylpropyl) -cyclohexylamine, N- (2-methylpentyl) -cyclohexylamine, N- (3- Methylpentyl) -cyclohexylamine, N- (3-methylpentyl) -cyclohexylar Ln, N- (1.1-Dimethylbutyl) -eye] ohexylamine, N- (2.2-dimethylbutyl) -cyclohexylamine, N- (3.3-dimothylbutyl) -cyclohexylamine, N- (2. 3-Dimethylbutyl) -cyclohexylamine, N- (1-ethylbutyl) -cyclohexylamine, N- (2-ethylbutyl) -cyclohexylamine, N-heptyl-cyclohexylamine, N- (1-methylhexyl) -cyclohexylamine, N- (2-methylhexyl) -cyclohexylamine, N- (3-methylhexyl) - "• cyclohexylamine, N- (I-ethylpentyl) -cyclohexylamine, N- (2-ethylpentyl) -cyclohexylamine, N- (3-ethylpentyl ) -cyclohexylamine, N-octylcyclohoxylamine, N- (1-methylpentyl) -cyclohexylamine, N- (2-methylheptyl) -cyclohexylamine, N- (3-methylhept yl) - · cyclohexylamine, N- (4-methylpentyl) -cyclohexylamine, N- (5-methylheptyl) -cycloh.-xylamine, N- (6-methylheptyl) -cyclohoxylamine, N- (1-ethylhexy L) -cyclohexylamine, N- (2- ^> s'thylhexyl) cyclohexylamine, N- (. '! - A "thy Lhexyl) -cyclohoxylajuine, N- (4-Xtl-ivlhcxyL) -cyclohexylamine, dicyolopentylamine, N-methylcyclopenuylamine, N, N-ethylcyclohexylamine , N-methylcyclobutylamine, N-methylcycloheptylamine and N-ethylcycloheptylamine.

Suitable araliphatic secondary amines are the listed aliphatic and cycloaliphatic amines in which one or more hydrogen on the hydrocarbons atoms are substituted by aryl radicals, e.g. the following:

Dibenzylamine, di- (2-phenylethyl) -amine, di (2-phenylpropyl) -amine, Di- (3-phenylpropyl) -amine, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine.

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As already mentioned above, the substituents of the secondary amine may be identical or different. she can also be connected to one another via a common bridge element. Examples of such cyclic amines are piperidine, pyrrolidine and derivatives as well as others. Nitrogen heterocycles.

The oxidizing agent used in the process according to the invention Oxygen or an oxygen-containing gas, in particular air, is used.

Suitable non-aqueous solvents in the invention Process aromatic hydrocarbons, such as benzene, Toluene, xylene, nitrobenzene, aliphatic see esters, alkyl ethers, lower alcohols such as methanol, ethinol and isopropanol, n-propanol, t-butanol, amyl alcohol, further chlorinated hydrocarbons, such as dichloromethane, chloroform, dichloroethane, trichloroethane, also anrotic solvents, such as dimethylformamide, Acetonitrile, dimethylacetcimide, dimethyl sulfoxide and hexamethylphosphoric acid triamide. As an aqueous solvent water / alcohol mixtures are particularly suitable. In individual cases, high yields are also achieved in pure water and selectivities achieved. In general, this is the reaction speed in water, however, less than in the above-mentioned non-aqueous solvents. Preferably be as a solvent aromatic hydrocarbons or. low alcohols or alcohol-water mixtures used.

The inventive method is carried out at temperatures in the range from 0 to 200 ⁰ C, preferably at 20 to 90 ° C. Temperatures above 90 ° C are mainly for economic and safety reasons, less

preferred.

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The method according to the invention is preferably used in Press oxygen or with oxygen partial pressures of carried out at least 0.1 bar. As expected, the rate of reaction increases with increasing oxygen pressure.

The inventive method can in principle after three well-known synthetic methods are carried out. Starting from secondary - \ min and carbon disulfide (Molar ratio 1.0 to 1.2: 1) one can use the reaction '' partner in the presence of oxygen or a: «:, oxygenated Gas and the metal-containing catalytic converter directly to the corresponding thiuram disulfi.c3 (Verfahrt-nsvariant e

(a)); but it is just as possible, at first only that Carbon disulfide with the secondary amine (molar ratio 0.9 to 1.1: 2.0 to 2.2) and then the reaction mixture obtained with carbon disulfide

(I ₇ O to 1.2 mol) in the presence of the metal-containing catalyst and of oxygen or the oxygen-containing gas (process variant

(b)); e. <is also possible, that of secondary amine and Dithiocarbamate formed as an intermediate product with carbon disulfide to isolate and then this dithiocarbamate with carbon disulfide (molar ratio 1.0: 1.0 to 1.2) in the presence of oxygen or an oxygen '"containing To implement gas and the metal-containing catalyst. (Process variant (c)).

The reaction time depends on the process conditions and ranges from a few minutes to several hours. Under optimal conditions with regard to temperature and oxygen pressure it is a few minutes.

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The process according to the invention is carried out in a simple manner in that the oxygen or the acidic :. Izoff-containing gas under the specified pressure and temperature conditions is pressed onto the reaction solution or passed into or through the reaction solution, which - according to the selected synthesis method - consists of solvent, secondary amine, catalyst and carbon disulfide, or from solvent, catalyst and dithiocarbairate or from that in the implementation of. secondary amine and carbon disulfide in the solvent obtained reaction mixture and catalyst. In most cases, as in the case of the Tetramet '; lylthiuramdisulfid, the end product immediately precipitates out of the reaction mixture and can be filtered off. In other cases, the desired end product is obtained on cooling or concentrating the reaction: mixture. Liquid products are obtained by distillation or ^(v r extractive workup in pure form.

In the technical implementation of the invention In the process, it is advantageous to recycle the mother liquor, and it is not necessary to always use fresh add metal-containing catalyst. For example, more than ten reaction cycles can be carried out with the same high yield can be carried out without any loss of catalyst activity being observed.

In the method according to the invention can be practical quantitative yields and seeactivities of more than 99 i can be achieved. The products fall in high purity an unri can as a rule without <! Purification of their destiny are fed.,

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Compared to the known two-step process, in which the dithiocarbamate is first synthesized, draws the one-stage process is economically viable, since none. Auxiliary materials are consumed. Compared to the the one-step process known from DE-AS 11 65 011, the process according to the invention has the vortex], that very simple and inexpensive catalysts can be used. It is also advantageous that in the technical implementation of the process according to the invention, soluble catalysts are used v / ground and can be recycled several times with the mother liquor without losing their activity, and that the yields are practically quantitative.

The thiuram disulfides to be produced according to the invention

are found in particular as vulcanization accelerators

for synthetic and natural rubber and as a fungicide use.

The following examples illustrate the invention:

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Example 1 (procedure according to claim la) In a 500 ml glass autoclave, which was equipped with a double jacket for the circulation of a heating fluid, a thermometer, a pressure measuring device and a stirrer, 13.5 g of dimethylamine and 43.5 mg of Ce III-nitrate · 6 H ₂ O (0.1 · 10 mol) dissolved in 100 g of isopropanol; 25.1 g of CS ~ (0.33 mol) were added to this solution (heating), the pale yellow clear solution was heated to 50 ° C., stirred vigorously and 1.7 bar of oxygen was injected. A strong uptake of oxygen was immediately registered (exothermic reaction) and the reaction solution became cloudy as a result of the deposition of tetramethylth luram disulfide. After just 15 minutes, no more oxygen was taken up, and the dimethylamine had reacted completely. The white crystalline precipitate was filtered off, washed with isopropanol and dried. This gave 35.7 g of a product which, in its analytical data (elemental ^{analysis, IR, 1} H-NMR, MS), agrees with tetramethylthiuram disulfide (TMTD) and whose purity was determined to be 100% by chromatography (see analysis) (mp .: 156 ° C). According to NMR analysis, the mother liquor contained a further 0.24 g of TMTD. Accordingly, the total output of the TMTD was 35.94 g, corresponding to 99.8% of theory. Th., Based on dimethylamine. The selectivity was also 99.8%.

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Example 2 : (Procedure according to claim 1 b) In a glass reaction vessel equipped with a reflux condenser and stirrer, a solution of 13.5 g (0.3 mol) of dimethylamine in 100 g of methanol was cooled with 12.4 g (0.16 mol ) Carbon disulfide reacted (exothermic reaction). Subsequently, the solution thus obtained was introduced into a 500 ml glass autoclave, 24.4 mg (0/1 x 10 ^-3 mol) Mn (OAc) 'added ₂ "3H0, heated to 50 ⁰ C and stirred vigorously at the same 1.7 bar oxygen was injected. Furthermore, 11.4 g (0.15 mol) of carbon disulfide were added during the reaction to the extent that dimethylamine was released during the reaction: a rapid uptake of oxygen was immediately recorded and the solution became cloudy as a result of the deposition of tetramethylithiuram disulfide finished after 44 min., after 47 min. the reaction was over (no further oxygen uptake, color change of the solution from violet-brown to pale yellow). The total yield of TMTD was 35.8 g, corresponding to 99.4% of theory.

Example 3: (procedure according to claim 1 c)

For the production of Dimethylaaimoniumdimethyldithiocarbamai; 30.4 g (0.4 mol) of carbon disulfide were obtained with cooling

to a solution of 36 g (0.8 mol) of dimethylamine in 100 g

Methanol added. The white precipitate formed was; filtered off, washed with cold methanol and dried and consisted of pure dimethylammonium dimethyldithiocarbamate.

24.9 g (0.15 mol) of this substance were in the reaction apparatus described in Example 1 in 100 g of methanol aufqe 1> ir, t and 12.2 g (0.16 mol) of carbon sulfur added. Diose Solution was with 24.4 mg (0.1 χ 10 mol) Mn (OAc);., - 4H0 added, heated to 50 ° C and with a pressure of 1.7 bar

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Vigorously stirred oxygen. A rapid uptake of oxygen was registered immediately and the solution became cloudy as a result of the deposition of tetramethylthiuram disulfide. The reaction was over after 52 minutes (no further oxygen uptake, the color of the solution changed from brown-violet to pale yellow), the white, finely crystalline precipitate was filtered off, washed and dried:
.35.5 <t tetramethylthiuram disulfide.

;) ie> Miittcrl.iuqe contained another 0.1 ?. g of this substance, so that: ¹ - the total yield of tetramethylthiuramdisulfide was 35.82 q , corresponding to 99.5% of theory. Th.

Example 4 : (Procedure according to approach 1 c) The procedure was as in Example 3, but the addition of carbon disulfide now took place during the reaction to the extent that dimethylair was released in the reaction. The addition of carbon disulfide was complete after 46 minutes, and the reaction was complete after 49 minutes. With this procedure, a total of 35.85 g of tetramethylthiuram disulfide were crhal; en, corresponding to 99.6% of theory. Th.

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The procedure was as in Example 1, but only 8.7 mg (0.02.10 ~ mol) cerium (III) nitrate is used. The oxygen uptake ended after 75 minutes. The total yield of TMTD was 35.89 g, corresponding to 99.7% of theory. Th.

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Examples 6 and 7 :

The procedure was as in Example 2, but different cerium compounds used as catalysts. The results of these tests are shown in the following table:

example
No-. catalyst
(Ο, Ο2 1Ο ~ ³ mol) reaction time
(min) TMTD
Yield , 2
, 5 6th
7th Ce (NHJ ₀ (NOJ,
4 2 3 6
(CH ₃ J ₂ NCS ₂ J ₃ Ce 78
72 99
99

Examples 8 and 9 :

In the following examples, other heavy metal compounds were used as catalysts. 13.5 g (0.3 mol) of dinethylamine, 23.6 g (0.31 mol) of carbon disulfide in 100 c: methanol were reacted with oxygen in the manner described in Example 1. The oxygen pressure was in each case 5 bar, the reaction temperature 50 ^° C. The catalyst used, the amount of the same, the reaction time and the yields of tetramethylthiuram disulfide are summarized in the following table:

Catalyst 10 mol reaction time TMTD yield h_. ( % of theory)

VOSO. • 5H "0 0.2 4 97.2

Mo0 ₂ (acac) ₂ . 0.4 9 96.4

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Example 10 :

In the reaction apparatus described in Example 1, 13.5 g (0.3 mol) of dimethylamine and 24.4 mg (0.1 ■ 10 mol) Mji (OAc) "· 4H" 0 dissolved in 100 g of isopropano3; to this Solution were added 22.8 g (0.3 mol) "carbon disulfide, the clear, dark brown solution is heated to 50 ° C., stirred vigorously and 1.7 bar oxygen is injected.

Under these conditions the reaction was complete after 90 minutes. TMTD was obtained in 98.6% yield.

Example 11 :

In the reaction apparatus described in Example 1, 21.9 g (0.3 mol) of diethylamine in a solution of 24.4 ItKI (0.1 · 10 ^-3 mol) Mn (OAc) ₂ · 4H ₂ O in 100 g Dissolved isopropanol; 23.6 g (0.31 mol) of carbon disulfide were added to this solution (heating), the clear, dark brown solution was quickly heated to 50 ° C., stirred vigorously and injected with 1.7 bar of oxygen. Oxygen uptake was immediately recorded; the reaction was over after 75 minutes (no further uptake of oxygen; solution turned light). When the reaction solution cooled, a white crystalline precipitate separated out, which was filtered off, washed with isopropanol and dried. In this way, 41.8 g of a product were obtained which, according to its analytical data (elemental analysis, IR ', NMR, MS, DC), corresponded to tetraethyllhiuramd sulfide (TETD). HNMR and chromatographic analysis has a purity of 100% (melting point: 72 ° C). The mother liquor contained a further 1.8 g of tetraethylthiuram disulfide, which could be isolated in pure form by concentrating the solution and washing the residue with isopropanol. Thus the total yield of tetraethylthiuram disulfide 4 was 3.6 g,

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accordingly.einer yield of 98.2% d. Th.

• Examples 12 to 18 :

The procedure was as in Example 6, but instead of Isopropanol used other solvents. The results

• these experiments are compiled in the following table:

example Solvent tel Response time TETD yield % of theory) Ver I.
ί No. (min) ( 97.5 I. 12th Methanol 55 98.2 i 13th Ethanol 85 98.0 14th n-propano] • 85 98.9 15th t-butanol 90 97.8 16 t-amyl alcohol 100 98.4 17th toluene 100 93.6 18th water 220 Examples 19 to 2:: 6 worked, but instead of It was as in example or other manganese-containing Mn (OAc) ₂ ~ 4H ; O'I <angan

bindings used. The results of these tests are summarized in the following table:

example catalyst reaction time TETD - From booty No. 0.1 '10 ~ ³ mol (min) (% of theory) 19th Mn powder 150 96.8 20th MnSO ₄ 205 96.5 21st MnO ₂ 140 97.9 22nd Mn 290 97.5 23 Mn ((C ₂ H ₅ J ₂ NCS ₂ ) ₂ 70 98.6 j

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Example 24 :

The procedure was as in Example 6, but instead of 8.6 mg (0.02 × 10 7 mol) of cerium (III) nitrate as the catalyst Manganese-II-acetate used. After 80 minutes the reaction was over completed; on cooling, tetraethylthiuram disulfide precipitated, which was filtered off, washed and dried; Final weight 41.7 g. The mother liquor contained a further 1.7 g of the product. Accordingly, the total yield of the tetraethylthiuram disulfide was 43.6 g corresponding to 97.7% d. Th.

Example 25 :

The procedure was as in Example 6, but the catalyst used was 43 mg (0.1 · 10 ^-3 mol) cerium-III-nitrate and the reaction was carried out at room temperature and an oxygen pressure of

1.7 bar carried out. Oxygen was immediately taken up registered and after a short time the solution became cloudy due to the separation of tetraethylthiuram disulfide. To The reaction was over for 75 minutes. The white precipitate was filtered off, washed and dried: 41.8 g of tetraethylthiuram disulfide. The mother liquor contained more

1.8 g of this product. Accordingly, the overall yield was

of ■ tetraethylthiuram disulfide 43.6 g, corresponding to 98.2% of theory

Examples 26 to 29 :

In the reaction apparatus described in Example 1 were 13.5 g (0.3 mol) of dimethylamine with a metal catalyst (see table) dissolved in 100 g of alcohol; to this were 23.6 g Added (0.31 mol) of carbon disulfide and the reaction mixture was oxidized with oxygen, the reaction temperature and the oxygen pressure being varied.

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example
No. catalyst
(Kf ³ ITDl) Reaction
te. "7> 2rature
( ^h O solvent O_ pressure
(bar) Reaction
Time
(min) Ursatz TMfD-
yield
(id.iti.) 26th
27
28
29 Cu (OAc) ₂ (0.1)
Mi (OAc) ₂ (0.1)
Cc (NO ₃ J ₃ (0.5)
Cu (OAc) ₂ (0.1) 25th
85
50
50 Icopropanol
/ ■ ieüunol
Isopropanol
Isqpropanol 5.0
Air, nonml-
, _Λ , pressure
10 bar 200
. 9
190
50 54.2
100
92.3
99.5 53.4
98.8
91.0 _:
98.6;
•

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These examples show that the process is broad Pressure and temperature range can be carried out with consistently high selectivity.

Example 30 :

In the reaction apparatus described in Example 1, 25.5 g (0.13 mol) of piperidine and 24.4 mg (0.1 · 10 mol) of Mn. (OAc) 2-4H ₂ O were dissolved in 100 g of isopropanol. 23.6 g (0.31 mol) of carbon disulfide were added to this solution, the clear, dark solution was heated to 50 ° C., stirred vigorously and 1.7 bar of oxygen were injected. After a short time, the solution became cloudy as a result of the deposition of dipentamethylene thiuram disulfide. The reaction was over after 60 minutes: the white precipitate was separated off, washed and dried, 46.8 g of a product being obtained whose analytical data (H-NMR, IR, MS, elemental analysis) corresponded to dipentamethylene thiuram disulfide (mp .: 132 ° C). The mother liquor contained a further 0.4 g of this product. Accordingly, the total yield of dipentamethylene thiuram disulfide was 47.2 g, corresponding to 98.3% of theory. Th.

Example 31 :

In the reaction apparatus described in Example 1, 20.2 g (0.2 mol) of di-n-propylamine and 24.4 mg (0.1'10 ~ mol) of Mn (OAc) ₂ -4H ₂ O were added to 100 g of isopropanol dissolved, then 16.0 g (0.21 mol) of carbon disulfide were added, the solution was heated to 50 ° C., oxygen was injected at 1.7 bar and stirred vigorously. An oxygen uptake was registered immediately, and the reaction had ended after 75 minutes. Concentration and cooling of the reaction solution gave 35.1 g of a white, crystalline product, which in his

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analytical data (elemental analysis, - "H-NMR, 'IR, MS) with Tetra-n-propylthiuram disulfide matched (yield 99.2% d. Th .; M.p .: 60 ° C).

Example 32 :

For the production of Tetraisopropylthiuramdisulfid were. 30.3 g (0.3 mol) diisopropylamine, 23.6 g (0.31 mol) carbon disulfide and 24.4 mg (Ο, 1 · 1Ο ~ ³ mol) Mn (OAc) ₂ «4H ₂ O reacted in 100 g of isopropanol in the manner described in Example 1. The oxygen pressure was 1.8 bar, the reaction temperature 50 ° C. and the reaction time 60 minutes. The white precipitate (36.4 g) formed on cooling the reaction solution consisted of the desired thiuram disulfide, which was obtained by physical and chemical analysis methods (elemental analysis, H- NMR, IR, MS) was determined. When the mother liquor was concentrated, a further 11.2 g of this substance precipitated, so that the total yield of tetraisopropylthiuram disulfide was 47.6 g, corresponding to 90.2% of theory. Th. (M.p .: 112 ° C).

Example 33 :

To prepare tetra-n-butylthiuram disulfide, 25.85 g (0.2 mol) of di-n-butylamine, 16.0 g (0.21 mol) of carbon disulfide and 24.4 mg (0.1 · ίο "" ³ ) Mn (OAc) ₂ -4H ₂ O in 100 g of isopropanol reacted with oxygen in the manner described in Example 1. The reaction temperature was 50 ° C., the oxygen pressure was 1.8 bar and the reaction time required for complete conversion was 10 b min. By working up the product solution by distillation, 40.2 g of tetra-n-butylthiuram disulfide were obtained as the oil formed (analytical determination by elemental analysis, " ¹ H-NMR, IR, MS) Yield: 98.5% of theory.

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Example 34;

To prepare tetra-i-butylthiuram disulfide, 25.85 g (0.2 mol) of di-i-butylamine, 16.0 g (0.21 mol) of carbon disulfide and 24.4 mg (0.1 x 10 ^-3 mol ) Mn (OAc) ₂ · .4H ₂ O in 100 g of isopropanol in the manner described in Example 1 to react with oxygen. The reaction temperature was 50 ° C., the oxygen pressure was 1.8 bar and the reaction time was 90 minutes. The white precipitate obtained when the reaction solution was concentrated consisted of the desired thiuram disulfide, which was obtained by physical and chemical analysis methods (TH-IMR, 1 ^] , MS, Elemental analysis). Yield: 36.8 g corresponding to 90.2% of theory (M.p. 71 ° C).

Example 35 ;

Di-tetramethylenethiuram disulfide was prepared in the manner described in Example 1 from 14.2 g (0.2 mol) of pyrrolidine and 16.0 g (0.21 mol) of carbon disulfide in the presence of 24.4 g (0.1 × 10 ^r3 mol) Mn (OAc) ₂ - 4 H ₂ O and 100 g of isopropanol, was prepared. The reaction ^{temperature was 50 °} C., the oxygen pressure was 1.8 bar and the reaction time was 30 minutes The white precipitate formed during the reaction was filtered off, washed and dried and consisted of aiu; roinom di-tetramethylene thiurandl sulfide (analytical determination by elemental analysis, U-NMR, '. IR, MS). The yield was 27.5 g, corresponding to 94.2% of theory. (M.p. 140 ° C).

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Example 36 :

For the preparation of NjN'-Diirethyl-N / N'-dicycloheJcyl-'thiuramäisulfid 22 _# 6 g (0.2 mol) N-ffethylcyclohexylamin and 16.0 g (0.21 mol) carbon disulfide in 100 g isopropanol in the presence of 24.4 mg (0.1 · 10 ^-3 mol) Mn (OAc) ₂ * 4H ₂ O in the manner described in Example 1 reacted. The oxygen pressure was 1.8 bar, the reaction ^{temperature 50 °} C. and the reaction time to complete conversion 85 min. The white precipitate already formed during the reaction was filtered off, washed and dried and was determined by chemical and physical analysis methods ^{(elemental analysis, 1 Il-} NMR, IR, MS) characterized as pure N, N ¹ -dimethyl-Ν, Ν ¹ -dicyclohexyl-thiuram disulfide (31.3 g). When the mother liquor was concentrated, a further 5.6 g of this substance precipitated, so that the total yield was 36.9 g, corresponding to 98.1% of theory. (M.p. 112 ° C). .

Example 37 ;

To prepare tetrabenzylthiuram disulfide, 39.5 g (0.2 mol) of dibenzylamine and 16.0 g (0.21 mol) of carbon disulfide were added in 100 g of methanol together with 24.4 mg (0.1 x 10 ~. Mol) of Mn ( OAc) - · 4Η_0 implemented in the manner described in Example 1. The oxygen pressure was 1.8 bar, the reaction temperature was 50 ^° C. and the reaction time was 3 h. The white precipitate formed during the reaction consisted of the desired thiuram disulfide, which was characterized by physical and chemical analysis methods (elemental analysis, H-NMR, IR, MS) (melting point 136 ^° C.). Yield 52.1 g corresponding to 95.6% of theory

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Claims (3)

Patent claims: araliphatic and / or cycloaliphatic hydrocarbon radicals substituted thiuram disulfide by reacting an appropriately substituted secondary amine with carbon disulfide in a solvent and in Presence of oxygen or an oxygen-containing one Gas and a metal-containing catalyst., Characterized in that the reaction with a secondary Amine with a pK value of -8 and at temperatures from 0 to 2pO ° C is carried out by a) Carbon disulfide and the secondary amine in one Molar ratio of 1.0 to 1.2: 1 in the presence of oxygen or an oxygen-containing gas and of the metal-containing catalyst is implemented, or b) first carbon disulfide and the secondary amine in a molar ratio of 0.9 to 1.1: 2.0 to 2.2 and then the reaction product obtained with 1.0 to 1.2 moles of carbon disulfide in the presence is converted by oxygen or an oxygen-containing gas and the metal-containing catalyst, or L - J Γ Ί - 2 -. A3GW31792 EN c) Carbon disulfide and the secondary AmLn in per se known Wise reacted in a molar ratio of 0.9 to 1.1: 2.0 to 2.2, the dithiocarbamate formed is isolated and then with carbon disulfide in a molar ratio of 1.0: 1.0 to 1.2 in the presence is converted by oxygen or an oxygen-containing gas and the metal-containing catalyst, wherein the metal-containing catalyst cerium, manganese, copper, molybdenum, vanadium or a derivative of mentioned metals or a mixture thereof is used. 2. The method according to claim 1, characterized in that the metal-containing catalyst in amounts of 0.01 up to 5 mmol, based on 1 mol of secondary amine or dithiocarbamate, is used. 3. The method according to claim 1 and 2, characterized in that that as a solvent an aromatic hydrocarbon, a lower alcohol., water or a mixture of the solvents mentioned is used. L J